Method of making a feed composition



Patented Aug. 19, 1952 METHOD oF MAKING A'FEED COMPOSITION James V. Rice, Cincinnati, Ohio, assignor to Buckeye Cotton Oil Company,-Memphis, Tenn.,

a corporation of Ohio,

No Drawing. Application January 18,1951, Serial No. 206,720 l This invention relates to the production of non-toxic cottonseed meal of improved value as animal feed and is a continuation-in-part of Serial No. 142,080, filed February 2, 1950.

Unprocessed cottonseed contain a yellow substance known as gossypol, found in the so-called pigment or resin glands which "-are scattered through themeat of'the seed. In processing the seed, hulls'are commonly removed first, and oil is then recovered from the meats, either by pressing or by extracting with a solvent. The remaining substantially oil-free cake, flake or meal is widely used as feed for livestock. As cattle feed, for example, its gossypol content is not important. On the other hand, gossypol is toxic to non-ruminant, single-stomached animals, such for example as swine and poultry, and as a result the meal can be'incorporated in I the rations of such animals with safety only if the freegossypol therein is low or if it is in some Way made non-toxic.

Purchasers of cottonseed meal for feeding purposes have by experience learned to associate a bright golden color with meal of high nutritive value, and to'associate adull muddy'color with less desirable meal. Bright colored meal is thereafter removal of the oil, with aniline (or other amines of the classes to be described) in the presence of water, as more fully described hereinaiter. g

In processing cottonseed, the dehulled meats are first rolled to a thin flaked form. The mechanical rolling or flaking does not rupture in appreciable amounts the pigment glands of the meats, most, of which survive this treatment intact. Oil is next separated from the meats, usually either by expression or by extraction with a solvent.

In the former case, either some form of hydraulic press, or a screw press, frequently known as an expeller, is commonly used. In the hydraulic press method, it is prevalentpractice to adjust the flakes to a moisture content of about 11-12 per cent Water, and then to heat or cook in order inter alia to reduce the moisture content to'an optimum for oil expression, e. g. about 5-6 per cent. The cooking is usually limited to an hour or.two and to a maximum temperature of about 230-240 FL, although-pressure cooking at is removed by hydraulic boxor cage presses,

19 Claims.

- oil-free.

leavinga press cake of some 5 or 6 per cent oil content, commonly referred to as substantially This press cake may be marketed as suchl, although more-frequently it is ground toa The cooking step in the above process is troduced for oil expression eificiency. Asgaresult of such heattreatment in the presence of water, the walls of the pigment glands are weak ened, so that they readily rupture when subjected to pressure or friction; Such rupture-liberates gossypol, which spreads'throughout; the flakes and appears to unite chemically'with the protein thereof, perhaps with the amino orthe carboxyl groups of the protein. Whatever the chemical nature of the change may be, it is well known that the toxicity of the resulting meal is reduced and that the free-gossypol content is likewise reduced, e. g. according to good United States practice to 0.1 per cent or less by weight. Exceptfor small-amounts which are carried out in the oil, most of the rest of the original gossypol remains in the finished meal in a non-toxic and diflicultly removable form, known as bound gossypol. The conversion of toxic free gossypol of intact pigment glands into non-toxic bound gossypol of ruptured glands is brought about and facilitated by heat, pressure and contact with water. Heating above about 240 F. is commonly avoided, however, since at such high temperatures more-or less denaturing of the protein takes place, with resulting decrease in nutritive value, and this is accompanied by adarkening and dulling of the color. 4 y In the screw press or expeller method of -removing oil, rolling and pre-cooking the moist meats are again employed, approximately the same temperature limitations being set in this case as in the case of hydraulic pressing. Due to the higher pressures. involved, cooling is usually required to counteract the frictional heat developed in screw pressing. .The resulting meal is commonly drier, of lower oil content, and since a larger proportion of the pigmentv glands are ruptured in thisprocess, the free gossypol content of the screw-pressed mealis lower.

Instead of usingpressure, the oil can be removed from flaked cottonseed meats by extraction with a low boiling solvent, for example with hexane or other saturated or unsaturated hydrocarbon solvents, of which pentane, heptane, cyclohexane, hexene, .heptene and benzene are examples, or with halogenated hydrocarbons of which carbon tetrachloride and trichlorethylene V 3 ized by heating and blowing with steam. In order to expel remaining water, a toasting step, involving heating the nearly dry flakes to, for

example, 230.2l0 F. is commonly practiced before the flakes are finally ground to a meal. the extraction process as 'described',ifewof the pigment glands are ruptured, and even after final toasting the free gossypolcontent is :fI'h'e above discussion explains why solvent-ex-- 'tractedvmeal, commonly containing upward of 0.06,to -0.1 per cent free gossypol, is'notasatis factoryfeed'for single-stomached animals such ."-'(-i.e; either wet or dry flakeswhich have been extracted but have not yet been toastedor 'ground) with ethyl-ether or some other goss'ypolsolvent is possible, but obviouslyuneconomical. Extracting oil from the flakes with a mixture of methanol anda -solvent hydrocarbon has' been proposed (1). $2,484,831), but Such a process involves operational difliculties in plant equipment and procedure. h I have found-that substantially oil-free cottonseedmeals or flakes which contain enoughfree gossypolto be toxic to single-stomached animals (l. e about 0.06 to 0.1;p'er cent or more of; free gossypoli can-be rendered harmless-to such anifinals and their free gossy-polcontent canbe reduced', by suitable treatment with a suitable aminein the presence of water at or aboveflnormal room temperature, as will appear hereinafter. I, have also found that addition of a suitable amine to the flaked oil-containing cottonseed meats;priorto the cooking step, in the hydraulic expression process described hereinbefore, substantially-, reduces the free gossypol content of i the cottonseed meats resultingfromthis process,

and consequently renders such meal harmless to single stomached animals. I

The process will firstbe described thereof will be described in later paragraphs. This treatment ruptures pigment glands, liberates {free gossypol and allows it to spread,

in a" simple. and preferred form using aniline, and variations throughout the cottonseed meat. The liberated.

gossypol isthuscontacted with andenabledto 1 combine with either the protein of the meat to form nontoxic"bound gossypol, or with aniline to form a non-toxiccompund therewith,- such as the wellknown and stable compound commonly.

V designated ,dianiline gossypolP I Either of these reactions would be; expected 'to detoxify the gossy-pol, and. I believe that both of them take V place. However, Ijdo not w sh to bebound byany theoretical explanation of the detoxification .which results from the treatment bymy process,

ceed 2403.1 1

4 both to detoxify and dry it, but I prefer to avoid more prolongedor drasticheating than is necessary. Specifically, I avoid heating sufiiciently to produce substantial denaturing of the protein 3 such as occurs at temperatures which much ex- In treating oil-containing cottonseed meats,

:the detoxification-is to take place during the mally be observed to avoid denaturing the proteinin the cottonseed flakes.

I have indicated that my detoxification process may be practiced withj ubstantially oil-free cottonseed meats ;or with cottonseed meats; from which-nogoil'has been :removed. Iprefer, however, to practice this" invention with meats from which the, oil hasbeen removed. inorderto-avoid adverse effectson-oil quality. v

' Thev amount ofarfilinerequired depends upon the-amountofjfreegossypol in themeats; to be treated: and upon other conditionsof treatment, such. as the proportion'of water-and thetemperature and time of;contact.- ,Under optimum; conditions, small amounts of. anilinevzare markedly eifecltive, such as 0.1 percent; basedupon-the dry weight ,of material to be ''treated. Larger amounts-can be more easily distributedzuniformly and are ;more beneficial, but-seldom'isgmore than one per centrequired, andingeneral; I prefer to use no more than.iswnecessary-ifor detoxification. Since, aniline-itself ;isi,toxic, ,it :is also essential that substantially all free aniline "be eliminated from the treated. cottonseediflakes. Therefore, I prefer, as a precautionaryv measure, inacase any exces of aniline .was;used over that-needed tofdetoxify the cottonseedv flakes, to contact the treated, flakes withxopen steam forta'bcutflve to v30-minutes, duringthelatter part offthe detoxification treatment, whereby. the excess :aniline is distilled ofi.

In order to distribute :the aniline uniformly throughoutthe materialand to makedetoxification eifective, I prefer-to disperse it in water before or while mixing it with the meal or flakes.

'material to atv least-140 F. for-a sufiicient time Thorough mechanical mixingiis required. i Vfater aids notonly in distributing the anilne'but' also in rupturing the walls of unruptured pigment glands and thus in liberating thegossypohwhich is prerequisite-to detoxifying it. The amount of water should be several times the weightofanb line, and in'general I find' itis desirable that it be at least four times the weight of aniline. Greater efiiciencyof detoxification .hasibeen 'observed with increasing ratios of water to-aniline upto at least 22:1,, Higher'ratiosmaybe employed if desired, buta practicallimit is'set because of the necessity of later driving offthe water in order to prepare. the material. for grinding, sacking, etc.

In treating solventeextracted flakes by 'my process, the flakes .caneither be wet with the .solventias after gravity drainage) or the solandwater can. be addedprior to' theheat' treatment by which the flakes are desolventized;the

solventand at least :a part .ofthewaterrbeing later d1stilled-ofi'.- In this case, it isLoften desir- "seesaw ablejto' condensev the distillate, collect the condensate as two immiscible layers, one of water and the other'oi solvent, and separatejthe solvent layer for use in extractingoil from a fresh batch ofcotton-seed flakes. To complete the drying and desolventizing, I usually toast the nearly dry aniline-treated flakes for 15-20 minutes at 230-240 F.,' but such toasting, should ,not be so prolonged nor at a temperature so Il'iigh'as to vreduce thenutritive'rvalue of the meal "by. denaturing prot'ein therein. Rapid, shortti me 10 minutes) toasting under pressure at as high as 260 hasbeen employed without harmful effect.

,As previously indicated, most of the pigment glands in solvent-extracted flakes remain intact. Mechanical rupture of these glands by attrition in the presence of aniline and watercan be practiced if' desired, and this is in some instances advantageous. v

The aniline treatment of the invention is especially valuable when applied to solventextracted cottonseed flakes, which normally contain unruptured pigment "glands and an amount iof'gfree goss'ypol' in excess of 0.1 per cent by weight, but itis not restricted thereto. It is applicable to any substantially oil-free cottonseed jmeals or'flakes high in free gossypol, irrespective of their previously oil-removal history. Furthermore, it is applicable to cottonseed meals or flakes, 'whether'pressed or solvent-extracted or otherwise rendered substantially oil-free, which contain less than about 0.06% to 0.1' per cent free goss'ypol, i. e. insu'filcient free gossypol to be toxic} but "sufllcient to interfere with the maximum nutritionalvalue of the productz'f Thus when the freegossypol content is less than about 0.06-t 0.1 per cent, the meal is no longer toxic to ls ingle-stomached animals, and yet a meal 'containingfior example, 0.06 percent free g'os'sypolis not'so good a feed as onecontaining "two-thirds this amount. The presence'of, or variationsin the amount of, free gossypol, at levels below about 0.04" per cent does not appear 'to affect demonstrably the nutritive valuelof the m'eal'fLWith non-toxic meal containing intermediate amounts of free'gossypol the nutritive value is markedly increased by 'the aniline-water 'treatmentof my'invention. The effect is similar to what might be expected if there were present in the untreated material some harmful ingredient other than gossypol which previous methods of detoxification have been unsuccessful in eliminating but which the aniline treatment succeeds in overcoming.

Hydraulicor screw-pressed cottonseed meals are illustrative of meal which normally contains less than 0.l per cent free gossypol, and which is benefited by the aniline-water treatment of the invention. The free gossypol content of such meal can in this way be reduced and the nutritive value thereof increased.

' i As hereinbefore indicated, the invention is useful notonlyin reducing free gossypol, in render- ;ing it non-toxic and in increasing nutritive value; itzalso improves the color of theresulting meal, making. it a bright golden yellow.'. This effect is especially marked when hydraulics-pressed or screwi-pressed' meal is dealt with, since'wone objectionable featureof such meals heretofore has beentheirp'dor color.-' The improvedcolor oi meal treated I by my process persists even when the heating involvedthereinis to temperatures as high as 260-270 F. 1. I V g Up to this point, theinvention'has been dei o-pheriylene dla'rnine 6 scribed in terms of treatment withanili'nepand water. Instead of aniline, however, there can be used any amine belonging to the group having the formulae .where each R belongs to the group consistingof "than 2 carbon atoms.

,Specificexamples of these types of amines are:

NH, NH;

aniline :a-napthylamine B-napthylemine a on; CH; oHz'f NH; CH! CHi t s NH; ovtoluldine 0-3 xylidine o 4 xylidino Y CHz CH: CH: v NH:

i 7 CH; 0113- NH; on,

i 7 NH nil-2 xylldine m-4 xylldine m-5 xylidine CH31 7 NH; NE,

NH;' C] Y 5 11-2 xylidine o-chloroaniline' m-chloroaniline NH NH, NH

7 2,5 dichloroaniline p -chloroaniline o-bromoaniline NH1 7 NH; NH;

. t I, v

Br r

' m-bronroanlline o-lodoanillne m-iodoaniline NH,

o-fluoroaniline m-fluoroaniline o-anisidine OCH: 1 OCIHS I NH. 7, NH]

penisidine o-phenetidine I o aminodiphenyl e a NIL m-phenylene dian'iine p-phenylene dlamin'e These amines can be used with satisfactory reseldom necessary to: use more than 0.15 per cent amino nitrogen. Furthermore, low boiling watersoluble organic solvents for gossypol can be used.

instead of water as dispersing liquids for the aniline orother amine, especially mixtures of such solvents with percent or more of water. Examples of such solvents are methyl, ethyl, propyl and isopropyl alcohols, acetone, methyl ethyl ketoneand dioxane. By the term "low boiling solvent I mean herein one having a boiling point not substantiallyabove 212 F. It shouldbe noted that these organic solvents, being volatile, are removedfrom the flakes by the heat treatment which'is a part of my .process, 1. e. by heating to a temperature above 140 F. but below that at which substantial denaturing of the cottonseed protein would take place. The function of the amine is, not to dissolve .or remove gossypol, but

to convert it into a non-toxic form, in which forin it remains in the finished product.

When solvent-extracted flakes are being treated according to that modification of .my process wherein a mixture of water-and water-soluble low boiling organic gossypol-solvent is used to disperse the aniline (or other amine), it is frequentlydesirable torecover both the oil-solvent and the gossypol-solvent for re-use. This can be accomplished by treating the drained spent flakesqwet with oil-solvent, according to my process, then desolventizing and drying by distillation, condensing the mixed vapors, allowing the condensate to stratify into two layers, (a) an oil-solvent layer and. (b) anaqueouslayer containing the organic gossypol-solvent, separating these two layers mechanically, and finally redistilling layer (12) in order by fractionation to recover the organic gossypol-solvent.

The following examples, in which all parts are byweight, illustrate without limiting the-invention. All figures for free gossypol content given herein and in the accompanying claimsv refer to results obtained by the analytical method of Smith, as described in the Analytical Edition of Ind. and Eng. Chem.,vol. 18, page 43, January 15, 19.46.

Example ,1.--Cottonseed "flakes, previously extracted' with hexane toa residual oil content of about 1% and containing 1.2% free gossypoL;

The flakes, hexane,

sultsi to'accomplish the purposesof thisinvention, 7 -"using them-in amounts equivalent in amino'nitrogen-to the" aniline usage previously described, e. g. in such'amounts thatthe weight of amino nitrogen is at least 0.015 per cent-of-the weight'of -the meal ol -flakes to be treated, although it is ing from repeating Example-'3,- but' substituting I other amines. for .toluidine, "the amount of amine 1 of water and. parts of, methanol.

f average; temperature at this 18 were, evaporated. The. flakes were then. ground toabright. golden yellow .meal, which .contained 0.04,%.;free.gos syp0l. Infthisexampletheweight qiaminonitrogen-in the aniline usedwas 0.1%

.7 of theweight ofdry vflakes. V I ,Similar results were obtained .byesimilaraaniline treatment ofa like batchof hexane-extracted dry ,flakes from which ..the...=hexane had .lpreviously been drivenroff.

.Example Zs-To .1000. parts (on adry basis) of hexaneeextracted zspent cottonseed flakes draline'd but. still wet with hexane andcontaining 1.00% free 'gossypol'on a solvent-free.- basis, there, was added a mixture of 2.09 parts of aniline, 8.8, parts The wet flakes were mixed at'70 -F. :to Fmfor 20 minutes in a jacketed mixer. They were then ,desolventized at 1609.1. and-finally toasted-for 20 minutes at 230 F., the heatbeing supplied by admitting steam to the jacket of the mixer. Free gossypol in the finished product was reduced to 0.07% by .thistreatment. In :thi's example, the weightiof amino nitrogenin the aniline used was about0.03%--o f the -weight of dry-flakes.

7 Example 3.41%) 1000 partsidry basis) ofhexane-extracted spent cottonseed flakes, drained but pol was reduced to 0.05'%-by this treatment. In

this example,,--the;weight: of amino nitrogen in the toluidines-was:0.- 1,% of the-weight of 'dryflakes,

It may beexpl'ained that in a series of runs, in each .of which the material, is first "mixed and thenrheated' by admitting steam to {the mixer cedingrun. Consequently: although; the charge temperature-rises somewhat-during mixing-the stage being usually 'betWeenflO FDand5100 -1 a Table .1: showsthefree gossypol content'resultin .each case bei'ngzsuch that-ath'e weight of amino nitrogen therein was 0.l of ith-e weight" of dry Example 4.--Into 1000 'parts of hydraulic pressed cottonseed meal containing 0.09%? free gossypol, there 'were-mixed 5 parts of aniline dis- :persed'in' 55"-'parts of water; The mi-Xture was held at"70 to 100 F.i=for 15 minutes; then heated to and'heldat-l230" F."for 15 minutes. "Thei'free gossypol in th'effinished'meal was0.04%.

Thee-aminoinitrogen irrthis example-was 0.075%

All *of 'the :mealsxzproduced' inrExamples to '4 were iofwa' bright: yellow :orzrgolde'n color. Table .2 below-illustratesrtheaappearance and the free gossypol content of flakes which,"after'solvent extractionr with hexane and subsequent gravity 2,607,687 9 i a aina e; were iec d to he i i -l v treatment,;;-samples being analyzed at various 10 increase the flake moisture.) The flakes were' dropped tothe lower kettle and heated to 220 F.

stages of the treatment. V, ior gm minutes after which they were formed and Table 2 Test No. 1' 2 3 4 5 .6 7 8 Percent Aniline a. 0. 4 0. 4 0. 4 0. 4 0. 57 a 0.57 0. 57 v 0. 57 Water to Aniline Ratio in Treatment Solution 4. 4 6. 6 8. 8 21. 9 4. 4 6. 6' 8. 8' l3. 2 Percent Free Gossypol alter 20 V U I min. mixing 1 Temp. 100 F 0. 92 0. 67 0. 62 0. 40 0. 14 0. 17 v 0. 15 Percent Free Gossypol after deso1-' ventizing Temp. 160 F 0.62 0.37 0. 26 0. 24 0.18 0. 08 0. 07v 0. Percent Free Gossypol after heatv .2

ing to 23 0. 46 0. 18 0. 13 0. v 0.12 0. 05 '0. 04' 0.06 Percent Free Gossypol after toast s g L f ing for'lO at 230 0. 48 0. 15 0. 13 I n 13 0. 12 0. 04 0. 03' 0.03 Meal Gol'or Bright Br. Br. Light Golden Gold. Gold. 7 Gold.

. v. 1 Yellow Yel. Yel. Brown Yellow Yel.

1 Calculated on weight of dry flakes.

It will be perceived that 'the free gossypol con-- tent decreases (a) with "higher aniline:flake's" ratio; (1)) with higherwatertaniline ratio: (c) v withjhigher temperature, although prolonging the heating at 230 F. produces no -appreciable that the. improvement in coloris' less marked as the i water content "of the aniline+water mixture increases.

The suitability of the detoxified mealiof invention" for feeding to. single-stomached' animalsi's' illustrated by the following feeding experiments which were carried out with guinea pigs under controlled conditions.

(gossypol free andwell'known to be a good food forfsuchanimals) was'used for comparativepur- ,1 Aiming} Fkd'H Doses. The basal rat on is shown in Table 3. Miais fizehcne gg g Table 7 V Y he Cottonseed (or soybean) iiie1 perer t 7 ercent Free GO$ YD 0.83s 0.102 10.015 Dehydratedalfalfa'nieaL 'do 25 qunqf TTTdQ-T"? 7. Wheat an-e". -!1- -9-,- 1Q The IOWBI per cent free gossypol found i th Hydrogenated vegetable .shortening e don 5 aniline-treated hydraulic meal indicates aniline Iodia'ed salt do 1 was definitely an aid in detoxifying the meal. rqli l me ne do 2 50 By employing the conditions of each of those Brewers yeast. do 2 of the specific examples, except for the substitu- Vitamin C, crystalline; g ./kilo of ration -1 Hon of the amines hereinbefore described for the Tame 4' belowshows the resum of feeding tests with Y It will be'understood that while my process Table 4 r is commonly applied to cottonseed meal or flakes, I I it IS applicable also to cottonseed meats in any Y other form h Q rge surfaces for con -j v a tact with the aniline-water mixture. When '7 i use the expression intimately contacting said Meal How Treated Aniline-HO I Meal: Percent Free Gcssy'pol. 1 0. 04 meats with hqmd treating agents of h 1Il-,' y fagg g g 60555; gg w n I e that the meats must be in such tie .o uinea igs,gms. 7 V A32. ri inmiweeks, gms.--. 153 -170 ,Ffi as to have arhlghv Surface tO'maSS-Y lnTve -fGai1 1to1n;eeg:s,tgms 28g 3 us, for example, the process is applicable bothjp N31 8: anim ls dieifilIII III 0 o 2 solvent @xtmcted flakes, l0 j e ground meal 1; Gmaoiieed/gmgainin weight. 5.33 I 5. 5 herefronn or to the meal obta ned by, grinding rWet reassessed flakes treated at F. to 100 F. with 1 pound of aniline in 14 pounds of water per 100 pounds of dry flakes weretoasted for 20 min. at 230 F. to remove hexane and water.

Ezcdmple 5. --I-lu1le d cottonseed :nieats were; rolled to a thickness of 0.014 inch. A portion of Soybean meal.

placed in a hydraulic press at 5200 p. s. i. for 20 minutes. Samples of the resultant meal were analyzed for gossypol content.

A second run was made following the same procedure as above except that a mixture of 1 part aniline and 8 parts water was added to 91 parts of cottonseed flakes in the cooker before the start of thi second run. No open steam was used during the heating of the flakes in this run, but open steam was employed during the last ten minutes of the cooking period to distill off the excess aniline. Samples of the meal from this second run were also analyzed for gossypol.

A comparison of the gossypol content of the two typesof meal are shown below.

aniline and mixed toluidinesthus employed, comparable results are achieved.

hydraulicor screw-pressed cakes. .Furthera more, thenon-toxic meal need not be used, alone stituents useful in animal; feeduto reduce. the

e go ypol content of the mixed feed we 11011..

mon es-'7 7 1i toxic: level. Thus, it is; within thesc'ope ofthe invention to; use the product as either aymajor or'a-minor constituent of'animal feed, whether for singleor multi-stomached animals. Furthermore, the invention is not limited to a process which produces cottonseed meal for use only as feed for domestic or other animals; the use of such meal for human consumption is also con-- 7 which process comprises the step ofdntimately contacting said meats with an amine belonging to the group consisting of NH; v

and"

' contentjof substantially oil-free cottonseed meats containing at least 0.04% free gossypol, which 7 process comprises the step of intimately contacting's'aid meats with an amine belonging'to the group consisting of and prising not more than two carbon-atoms,- in the presence of a dispersing-liquid-of the'class consisting of water and mixturesof-water with a lowboiling water-soluble organicsolvent "forgossypol and heating" the mixture to a tempera tui'e'in excess of 140-F but insufficient to cause substantial denaturing of proteinint-he meats, A g

the amine being in such amount-that theweight of amino nitrogen therein isfrom" 0.015%"tofl 0.15 of'the weight of said meats; andthe' wei ht of dispersing liquid being at-least four times the weight 'ofsaid' amine.

3. A process for substantially detoxifying cottonse'edi flakes containing fre'e gossypol; which V 12*". 7 comprises intimately; contacting said-flakes t6 on removal with 7 an amine" belonging to 'tlia group consisting of 1 and wherein each R is selected from the group: eon

amino 'benzyl, thealkyl radical in all cases como prising not more than. two, carbon-atoms, 'in'the presence of a dispersing liquid of the class consisting of water and mixtures of water with a low" boiling water-soluble organic solvent for gossypol, heating the mixture to a temperature in excess of F. but insufficient to causesubstantial denaturing of protein in the flakes, and pressing the oil from the flakes.

4. A process ofiinprovingthe nutritive value v of substantially oil-free cottonseed meats 'con- 1 taining free gossypol in an amount sufiicientltoj be harmful when fedto singIe-stomachedammals, which: process comprises 'wettingandjintiinately contacting said meats with aniline in'tl'ie p'i'es'en an of water, and heating said wetted meats, thereby' reducing the free gossypol c'onte'nt'th'eieof.

5'. A process of detoxifying oil-containingfco't tonseed meats containing free gossypol which" comprises wetting and intimately contacting said meatswith aniline inith'e' presence of water. heating said wetted meats, thereby reducing the free gossypol. content thereof; and contacting said) meatswith open"stean'1 whereby any'ex'cess an'i line is distilled off. j

6. A processof improving the nutritive value of substantially oil-free *cotton'seed'rmeats contain" ing" free gossypol in an amount sufficient to be 7 harmful when fed" to -single-stomached animals; which process comprises-wettingand intimately contacting said meats with aniline in the presence of water; heating-said wettedmeats,tther.eby're-" ducingthe free gossypol content thereof, and contacting said meats with open steam-whereby any excess aniline is distilled 01f.

aniline in the presence of water and'subje'cting said meats, in the presence'of anilineand water,

to attrition sufi'icient to rupture said glands;

9; A processof detoxifying solvent extracted cottonseed flakes'comprising'free gossypol; which process comprises intimately contacting said flakes with from eona 0.01- times theirweig'lit of aniline in the presence, ofan amount of'wafier at:leastfourtimes the weight of -the anilinegand heating v the mixture at about M0"- to 240 F; 'fora time suflicient-todetoxify thafree gos'sypol and 13 insufficient to eflect substantial denaturing of protein.

10. A process of detoxifying solvent-extracted cottonseed flakes containing free gossypol in an amount harmful for animal feeding purposes. which process comprises intimately contacting said flakes, wet with the extraction solvent, with aniline in the presence of water, and distilling off substantially all solvent and at least part of the water at a temperature in excess of 140 F. but insufficient to cause substantial denaturing of protein in the flake.

11. A process of rendering cottonseed meal suitable as feed for single-stomached animals, which process comprises the steps of intimately contacting hexane-extracted cottonseed flakes, wet with hexane, with an amount of aniline equal to from 0.1 per cent to 1.0 per cent of the flakes on a dry basis and an amount of water equal to at least four times the weight of the aniline; distilling off the hexane and at least part of the water from the mixture by heating said mixture to a temperature above 140 F. and insufficient to cause substantial denaturing of protein; condensing the distillate; collecting the condensate as two immiscible liquid layers, one of water and the other oi. hexane; and separating the hexane layer for use in extractingoil from another batch of unextracted cottonseed flakes.

12. A method of improving the color of cottonseed meal which comprises mixing (a) substantially oil-free cottonseed meats which have a high ratio of surface to mass and which contain intact pigmentglands, (b) aniline amounting to at least 0.1 per cent of the weight of said meats, and water amounting to at least four times the weight of the aniline; heating the mixture to at least 140 F.; driving off the greater part of the water,

- the cottonseed meal and an amine belonging to and heating the nearly dry remaining material to a temperature not exceeding 260 F., thereby rupturing pigment glands and dispersing at least a portion of the gossypol content thereof throughout the material.

13. A method of improving the color of cottonseed meal derived from cottonseed meats which comprises mixing (a) oil-containing cottonseed meats which have a high ratio of surface to mass, (b) aniline amounting to at least 0.1 per cent of the weight of said meats, and (0) water amounting to at least four times the weight of the aniline; heating the mixture to at least 140 F., thereby rupturing pigment glands and dispersing the gossypol content thereof throughout the material; driving off the greater part of the water and pressing the oil from the meats, whereby substantially oil-free cottonseed meal is obtained.

14. An animal feed of improved nutritive value comprising cottonseed meal containing dianiline gossypol derived from the original free gossypol content of the cottonseed from which the meal was prepared and a residue of free gossypol in I non-toxic amount.

15. A substantially oil-free cottonseed meal of improved nutritional value whose gossypol content is substantially wholly non-toxic dianiline gossypol.

16. Cottonseed meal of improved nutritional value whose gossypol content exists, as a nontoxic aniline compound of gossypol and free gossypol in non-toxic amount, the free gossypol being less than 0.1 per cent by weight of the meal.

1'7. A cottonseed meal of improved color comprising a non-toxic compound of gossypol derived from the original free gossypol content of the group consisting of and wherein each R is selected from the group con-' sisting of hydrogen, alkyl, halogen, alkoxy, phenyl, amino phenyl, alkyl amino phenyl and. amino benzyl, the alkyl radical in all cases comprising not more than two carbon atoms, and a residue of free gossypol in non-toxic amount.

18. A process of improving the nutritive value of cottonseed meats containing free gossypol which comprises intimately contacting said meats with aniline in the presence of water to react REFERENCES CITED The following references are of record in the flle of this patent:

UNITED STATES PATENTS Number Name Date 1,553,634 Sawyer Sept. 15, 1925 2,064,158 Harrel et a1. Dec. 15, 1936 2,316,014 Alcott Apr. 6, 1943 2,484,831 Hutchins et a1. Oct. 18, 1949 

1. A PROCESS FOR IMPROVING THE NUTRITIVE VALUE OF COTTONSEED MEATS CONTAINING FREE GOSSYPOL WHICH PROCESS COMPRISES THE STEP OF INTIMATELY CONTACTING SAID MEATS WITH AN AMINE BELONGING TO THE GROUP CONSISTING OF 